The present invention relates to an oxidation dye composition for keratin fibers, and in particular human keratin fibers such as the hair. The inventive composition comprises at least one oxidation dye precursor, optionally one or more couplers, and at least one anionic amphiphilic polymer containing at least one hydrophilic unit and at least one allyl ether unit containing a fatty chain.
It is known to dye keratin fibers, and in particular human hair, with dye compositions containing oxidation dye precursors, generally known as xe2x80x9coxidation basesxe2x80x9d, in particular ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic bases.
Oxidation dye precursors are compounds that are initially colorless or only slightly colored, which develop their dyeing power on the hair in the presence of oxidizing agents, leading to the formation of colored compounds. The formation of these colored compounds results either from an oxidative condensation of the xe2x80x9coxidation basesxe2x80x9d with themselves or from an oxidative condensation of the xe2x80x9coxidation basesxe2x80x9d with color modifier compounds, or xe2x80x9ccouplersxe2x80x9d, which are generally present in the dye compositions used in oxidation dyeing and are represented more particularly by meta-phenylenediamines, meta-aminophenols, meta-diphenols, and certain heterocyclic compounds.
The variety of molecules used, which include, on the one hand, xe2x80x9coxidation basesxe2x80x9d and, on the other hand, xe2x80x9ccouplersxe2x80x9d, allows a very broad range of colors to be obtained.
In order to localize the oxidation dye product to application on the hair so that it does not run down the face or outside of the areas which one wishes to dye, use has been made prior to this point in time of traditional thickeners such as crosslinked polyacrylic acid, hydroxyethylcelluloses, waxes or alternatively mixtures of nonionic surfactants with an HLB (hydrophilic-lipophilic balance) which, when suitably chosen, bring about a gelling effect when they are diluted with water and/or surfactants.
However, the inventors have observed that the ingredients of the traditional thickener, surfactant and solvent type generally decrease the uptake of the dye on the fibers, which is reflected by a dull shade and also by the necessary use of more dye, solvent and/or surfactants to solubilize the dye if it is desired to obtain an intense shade. Moreover, the inventors have also observed that after mixing with an oxidant, the dye compositions containing the oxidation dye precursor or precursors and optionally the coupler or couplers, and also the above-mentioned ingredients, lost some of their gelled nature and consequently led to undesirable running.
Now, after considerable research conducted in this direction, the inventors have discovered that it is possible to obtain oxidation dye compositions (after mixing with the oxidant) which do not run and therefore remain better localized at the point of application, and which also make it possible to obtain more chromatic (more luminous) shades while at the same time being appreciably intense, if an effective amount of an anionic amphiphilic polymer containing at least one hydrophilic unit and at least one allyl ether unit containing a fatty chain, are introduced (i) either into the composition containing the oxidation dye precursor or precursors and optionally the coupler or couplers [or composition. (A)], or (ii) into the oxidizing composition [or composition (B)], or (iii) into both compositions at the same time.
For purposes of the present invention, the chromaticity (luminosity) is defined by the value c* in the L*, a*, b* calorimetric notation system of the Commission Internationale de I""Eclairage (C.I.E.) [International Lighting Commission]. This value (c*) is equal to the square root of the sum a2+b2 (+a is red, xe2x88x92a is green, +b is yellow, xe2x88x92b is blue). The shade is proportionately more luminous the higher the value of c*.
In this system of notation, L* defines the intensity of the shade. The shade is proportionately more intense the smaller the value of L* (0=black, 100=white).
These discoveries form the basis of the present invention.
A subject of the present invention is thus an oxidation dye composition for keratin fibers, in particular for human keratin fibers such as the hair, this composition comprising, in a medium which is suitable for dyeing, at least one oxidation dye precursor (oxidation base) and, where appropriate, one or more couplers, which composition is characterized in that it also contains at least one anionic amphiphilic polymer containing at least one hydrophilic unit and at least one allyl ether unit containing a fatty chain.
By means of the present invention, it is also possible, advantageously, to reduce the consumption of surfactants, or even to dispense with them altogether.
The present invention also makes it possible to decrease the amount of active coloring materials used in the dye compositions, relative to conventional techniques known in the prior art.
Another subject of the present invention relates to a ready-to-use composition for dyeing keratin fibers, which contains at least one oxidation dye precursor and optionally at least one coupler, and at least one anionic amphiphilic polymer containing at least one hydrophilic unit and at least one allyl ether unit containing a fatty chain, and an oxidizing agent.
The invention is also directed towards a process for dyeing keratin fibers, and in particular human keratin fibers such as the hair, this process comprising applying to these fibers at least one composition (A1) containing, in a medium which is suitable for dyeing, at least one oxidation dye precursor and optionally at least one coupler, in combination with at least one anionic amphiphilic polymer containing at least one hydrophilic unit and at least one allyl ether unit containing a fatty chain, the color being developed at alkaline, neutral or acidic pH using an oxidizing agent which is mixed with the composition (A1) only at the time of use or which is present in a composition (B1) that is applied sequentially without intermediate rinsing.
The invention is also directed towards a variant of the above process, which comprises applying to the fibers at least one composition (A2) containing, in a medium which is suitable for dyeing, at least one oxidation dye precursor and optionally at least one coupler, and doing so in the presence or absence of an anionic amphiphilic polymer containing at least one hydrophilic unit and at least one allyl ether unit containing a fatty chain, the color being developed at alkaline, neutral or acidic pH using an oxidizing composition (B2) which contains an oxidizing agent and an effective amount of at least one anionic amphiphilic polymer containing at least one hydrophilic unit and at least one allyl ether unit containing a fatty chain. Composition (B2) is mixed with composition (A2) only at the time of use or is applied sequentially without intermediate rinsing.
Another subject of the invention is multi-compartment dyeing devices or xe2x80x9ckitsxe2x80x9d, a first compartment of which contains at least one oxidation dye precursor, optionally at least one coupler, and at least one anionic amphiphilic polymer containing at least one hydrophilic unit and at least one allyl ether unit containing a fatty chain, and a second compartment of which contains an oxidizing agent.
According to another variant, the present invention also includes multi-compartment dyeing devices or xe2x80x9ckitsxe2x80x9d, a first compartment of which contains at least one oxidation dye precursor, optionally at least one coupler, and does so in the presence or absence of anionic amphiphilic polymer containing at least one hydrophilic unit and at least one allyl ether unit containing a fatty chain, and a second compartment of which contains an oxidizing agent and an effective amount of at least one anionic amphiphilic polymer containing at least one hydrophilic unit and at least one allyl ether unit containing a fatty chain.
The invention also relates to the use of the oxidation dye composition defined above or a multi-compartment dyeing device or xe2x80x9ckitxe2x80x9d as defined above in, order to dye human keratin fibers such as the hair.
Other characteristics, aspects, objects and advantages of the invention will become even more apparent on reading the description and the examples which follow.
The anionic amphiphilic polymers containing at least one hydrophilic unit and at least one allyl ether unit containing a fatty chain which are used according to the invention are preferably selected from those in which the hydrophilic unit contains an ethylenic unsaturated anionic monomer, more particularly a vinyl carboxylic acid and most particularly an acrylic acid, a methacrylic acid or mixtures thereof, and whose allyl ether unit containing a fatty chain corresponds to the monomer of formula (I) below:
CH2xe2x95x90CRxe2x80x2CH2OBnRxe2x80x83xe2x80x83(I)
in which Rxe2x80x2 denotes H or CH3, B denotes the ethylenoxy radical, n is zero or denotes an integer ranging from 1 to 100, R denotes a hydrocarbon radical selected from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl radicals which contain from 8 to 30 carbon atoms, preferably from 10 to 24, and even more particularly from 12 to 18 carbon atoms.
A unit of formula (I) more particularly preferred according to the present invention is a unit in which Rxe2x80x2 denotes H, n is equal to 10 and R denotes a stearyl (C18) radical.
Anionic amphiphilic polymers of this type are described and prepared, according to an emulsion polymerization process in European Patent EP-0,216,479 B2, the disclosure of which is hereby incorporated by reference.
Among these anionic amphiphilic polymers, polymers formed of 20 to 60% by weight acrylic acid and/or methacrylic acid, of 5 to 60% by weight lower alkyl (meth)acrylates, of 2 to 50% by weight allyl ether containing a fatty chain of formula (I), and of 0 to 1% by weight of a crosslinking agent which is a well-known copolymerizable polyethylenic unsaturated monomer, for instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate and methylenebisacrylamide, are more particularly preferred according to the invention.
Among the latter, crosslinked terpolymers of methacrylic acid, of ethyl acrylate, of polyethylene glycol (10 EO) ether of stearyl alcohol (Steareth 10), in particular those sold by the company Allied Colloids under the names SALCARE SC 80 and SALCARE SC90, which are aqueous emulsions containing 30% of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate and of steareth-10 allyl ether (40/50/10), are most particularly preferred.
The anionic amphiphilic polymers containing at least one hydrophilic unit and at least one allyl ether unit containing a fatty chain according to the invention are preferably used in an amount which may range approximately from 0.05 to 10% by weight relative to the total weight of the dye composition applied to the fibers. More preferably, this amount varies approximately from 0.2 to 5% by weight.
The oxidation dye precursors which can be used in the context of the present invention are selected from those known conventionally in oxidation dyeing and among which mention may be made in particular of:
para-phenylenediamines of formula (II) below, and acid-addition salts thereof: 
xe2x80x83in which:
R1 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical or a 4xe2x80x2-aminophenyl radical,
R2 represents a hydrogen atom or a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical or a C2-C4 polyhydroxyalkyl radical,
R3 represents a hydrogen atom, a halogen atom such as a chlorine atom, or a C1-C4 alkyl radical, a sulpho radical, a carboxyl radical, a C1-C4 monohydroxyalkyl radical or a C1-C4 hydroxyalkoxy radical, and
R4 represents a hydrogen atom or a C1-C4 alkyl radical.
Among the para-phenylenediamines of formula (II) above, mention may be made more particularly of para-phenylenediamine, para-toluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-paraphenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(xcex2hydroxyethyl)-para-phenylenediamine, 4-amino-N,N-bis(xcex2-hydroxyethyl)-3-methylaniline, 4-amino-3-chloro-N,N-bis(xcex2-hydroxyethyl)aniline, 2-xcex2-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(xcex2-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N-(xcex2-hydroxyethyl)-para-phenylenediamine, N-(xcex2,xcex3-dihydroxypropyl)-para-phenylenediamine, N-(4xe2x80x2-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine and 2-xcex2-hydroxyethyloxy-para-phenylenediamine, and acid-addition salts thereof.
Among the para-phenylenediamines of formula (II) above, para-phenylenediamine, para-toluylenediamine, 2-isopropyl-para-phenylenediamine, 2-xcex2-hydroxyethyl-para-phenylenediamine, 2-xcex2-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine. 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine and 2-chloro-para-phenylenediamine, and acid-addition salts thereof, are most particularly preferred.
bis(phenyl)alkylenediamines corresponding to formula (III) below, and acid-addition salts thereof: 
xe2x80x83in which:
Q1 and Q2, which may be identical or different, represent a hydroxyl radical or NHR8 in which R8 represents a hydrogen atom or a C1-C4 alkyl radical,
R5 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical or a C1-C4 aminoalkyl radical in which the amino residue may be substituted,
R6 and R7, which may be identical or different, represent a hydrogen or halogen atom or a C1-C4 alkyl radical,
W represents a radical taken from the group consisting of the following radicals: xe2x80x94(CH2)nxe2x80x94; xe2x80x94(CH2)mxe2x80x94Oxe2x80x94(CH2)mxe2x80x94; (CH2)mxe2x80x94CHOHxe2x80x94(CH2)mxe2x80x94; and 
xe2x80x83in which n is an integer from 0 to 8 and m is an integer from 0 and 4.
Among the bis(phenyl)alkylenediamines of formula (III) above, mention may be made more particularly of N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)-1,3-diamino-2-propanol, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)ethylenediamine, N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4-aminophenyl)tetra-methylenediamine, N,Nxe2x80x2-bis(4-methylaminophenyl)tetra-methylenediamine, N,Nxe2x80x2-bis(ethyl)-N,Nxe2x80x2-bis(4xe2x80x2-amino-3xe2x80x2-methylphenyl)ethylenediamine, as well as acid-addition salts thereof.
Among these bis(phenyl)alkylenediamines of formula (III), N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)-1,3-diamino-2-propanol or one of the acid-addition salts thereof is particularly preferred.
para-aminophenols corresponding to formula (IV) below, and acid-addition salts thereof: 
xe2x80x83in which:
R9 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a (C1-C4)alkoxy-(C1-C4)alkyl radical, a C1-C4 aminoalkyl radical or a (C1-C4)hydroxyalkyl(C1-C4)aminoalkyl radical;
R10 represents a hydrogen or fluorine atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a C1-C4 aminoalkyl radical, a C1-C4 cyanoalkyl radical or a (C1-C4)alkoxy(C1-C4)alkyl radical, it being understood that at least one of the radicals R9 or R10 represents a hydrogen atom.
Among the para-aminophenols of formula (IV)-above, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol and 4-amino-2-(xcex2-hydroxyethylaminomethyl)phenol, and acid-addition salts thereof, may be mentioned more particularly.
the ortho-aminophenols which can be used as oxidation bases in the context of the present invention are selected in particular from 2-aminophenol, 2-amino-1-hydroxy-5-methylbenzene, 2-amino-1-hydroxy-6-methylbenzene and 5-acetamido-2-aminophenol, and acid-addition salts thereof.
the heterocyclic bases which can be used as oxidation bases in the context of the present invention are selected in particular from pyridine derivatives, pyrimidine derivatives and pyrazole derivatives, and acid-addition salts thereof.
Among the pyridine derivatives, mention may be made more particularly of the compounds described, for example, in patents GB-1,026,978 and GB-1,153,196, the disclosures of which are hereby incorporated by reference, such compounds being, for instance, 2,5-diaminopyridine and acid-addition salts thereof.
Among the pyrimidine derivatives, mention may be made more particularly of the compounds described, for example, in German patent DE-2,359,399 or Japanese patents JP-88-169,571 and JP-91-333,495, the disclosures of which are hereby incorporated by reference, such compounds being, for instance, 2,4,5,6-tetraaminopyrimidine and 4-hydroxy-2,5,6-triaminopyrimidine and acid-addition salts thereof.
Among the pyrazole derivatives, mention may be made more particularly of the compounds described in German patents DE-3,843,892 and DE-4,133,957 and PCT patent applications WO-94/08969 and WO-94/08970, the disclosures of which are hereby incorporated by reference, such compounds being, for instance, 4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole and 4,5-diamino-1-(4xe2x80x2-chlorobenzyl)pyrazole, and acid-addition salts thereof.
According to the invention, the oxidation base or bases preferably represent from 0.0005 to 12% by weight approximately relative to the total weight of the composition (A) and even more preferably from 0.005 to 6% by weight approximately.
The couplers which can be used in the dyeing process according to the invention are those used conventionally in oxidation dye compositions, i.e., meta-phenylenediamines, meta-aminophenols and meta-diphenols, mono- or polyhydroxylated naphthalene derivatives, sesamol and derivatives thereof and heterocyclic compounds such as, for example, indole couplers, indoline couplers, pyridine couplers and acid-addition salts thereof.
These couplers may be selected in particular from 2-methyl-5-aminophenol, 5-N-(xcex2-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(xcex2-hydroxyethyloxy)benzene, 2-amino4-(xcex2-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol, xcex1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one and 1-phenyl-3-methylpyrazol-5-one, and acid-addition salts thereof.
When they are present, these couplers preferably represent from 0.0001 to 10% by weight approximately relative to the total weight of the composition (A), and even more preferably from 0.005 to 5% by weight approximately.
In general, the acid-addition salts of the oxidation bases and couplers are selected in particular from the hydrochlorides, hydrobromides, sulphates, tartrates, lactates and acetates.
The composition (A) may also contain, in addition to the oxidation dye precursors defined above and the couplers combined optionally therewith, direct dyes to enrich the shades with glints. These direct dyes may then be selected in particular from nitro, azo and anthraquinone dyes.
The composition (A) and/or the composition (B) also more particularly contains at least one cationic or amphoteric substantive polymer as defined on pages 3 and 4 of European patent application EP-0,673,641 A1, the disclosure of which is hereby incorporated by reference, and for which it is advantageously preferred to use:
the quaternary polyammonium polymers prepared and described in French patent 2,270,846, the disclosure of which is hereby incorporated by reference, containing repeating units corresponding to formula (V) below: 
and whose molecular weight, determined by gel permeation chromatography, ranges from 9500 to 9900;
the quaternary polyammonium polymers prepared and described in French patent 2,270,846, the disclosure of which is hereby incorporated by reference, containing repeating units corresponding to formula (VI) below: 
and whose molecular weight, determined by gel permeation chromatography, is about 1200.
The medium for composition (A) which is suitable for dyeing is preferably an aqueous medium containing water and which optionally contains cosmetically acceptable organic solvents including, more particularly, alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol and phenylethyl alcohol, glycols or glycol ethers such as, for example, the monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or ethers thereof such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol and diethylene glycol alkyl ethers such as, for example, diethylene glycol monoethyl ether or monobutyl ether, in concentrations of approximately from 0.5 to 20% and preferably approximately from 2 to 10% by weight relative to the total weight of the composition.
The composition (A) may also contain an effective amount of other agents, previously known elsewhere in oxidation dyeing, such as various common adjuvants, for instance sequestering agents, hair conditioners and in particular silicones, preserving agents, opacifiers, etc., and optionally anionic, nonionic or amphoteric surfactants or mixtures thereof.
The composition (A) may also contain antioxidants. These may be selected in particular from sodium sulphite, thioglycolic acid, thiolactic acid, sodium bisulphite, dehydroascorbic acid, hydroquinone, 2-methylhydroquinone, tert-butylhydroquinone and homogentisic acid, and they are then generally present in amounts ranging approximately from 0.05 to 1.5% by weight relative to the total weight of the composition.
Obviously, a person skilled in the art will take care to select the optional additional compound or compounds mentioned above, such that the advantageous properties intrinsically associated with the dye composition according to the invention are not, or are substantially not, adversely affected by the addition or additions envisaged.
In the composition (B), the oxidizing agent is preferably selected from urea peroxide, alkali metal bromates or ferricyanides, and persalts such as perborates, percarbonates and persulphates. The use of hydrogen peroxide is particularly preferred.
The composition (B) advantageously contains an aqueous hydrogen peroxide solution whose titre may range, more particularly, approximately from 2.5 to 40 volumes, and even more preferably approximately from 5 to 20 volumes.
The pH of the ready-to-use composition applied to the keratin fibers [composition resulting from mixing the dye composition (A) and the oxidizing composition (B)] generally ranges from 4 to 11. The pH preferably ranges from 6 to 10, and may be adjusted to the desired value using acidifying or basifying agents that are well known in the state of the art in the dyeing of keratin fibers.
Among the basifying agents which may be mentioned, by way of example, are aqueous ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and derivatives thereof, sodium hydroxide, potassium hydroxide and compounds of formula (VII) below: 
in which R is a propylene residue optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; R11, R12, R13 and R14, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.
The acidifying agents are conventionally, by way of example, inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids is such as tartaric acid, citric acid or lactic acid, and sulphonic acids.
The dyeing process according to the invention preferably comprises applying a mixture, prepared at the time of use from the compositions (A) and (B) described above, onto the wet or dry keratin fibers and in leaving it to act for an exposure time preferably ranging from 1 to 60 minutes approximately, and more preferably from 10 to 45 minutes approximately, rinsing the fibers, optionally washing them with shampoo and rinsing them again and drying them.